Carbon Disulfide → Dicyanoketene Dimethyl Thioacetal

HRID 1586951Notes

Reaction equation

HRID 1586951 reaction equation
[CH3:1][O-].[Na+].[Na].[C:5](#[N:9])[CH2:6][C:7]#[N:8].[C:10](=[S:12])=S.S([O:18][CH3:19])(OC)(=O)=O>C(O)C>[CH3:1][O:18][C:19]([S:12][CH3:10])=[C:6]([C:5]#[N:9])[C:7]#[N:8]

Participants

7

Reactant 5

HCID 6348Carbon DisulfideHCID 6497Dimethyl SulfateHCID 8010MalononitrileHCID 5360545Sodium2×HCID 10942334Sodium Methoxide

Product 1

HCID 14150559Dicyanoketene Dimethyl Thioacetal

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

To a sodium methylate solution of 2.3 g (0.1 mol) of sodium and 41 g of ethanol, 6.6 g (0.1 mol) of malononitrile (melted) was instilled under exclusion of moisture within 5 minutes at room temperature with stirring and then stirred for another 5 minutes at room temperature. The resultant suspension was cooled to 15° C. and, at this temperature, solutions of 7.6 g (0.1 mol) of carbon disulfide in 36 g of ethanol and 2.3 g (0.1 mol) of sodium in 41 g of ethanol were added within 60 minutes from two injection syringes operated synchronously. During the addition, a clear yellow-green solution formed, which was stirred for another 60 minutes. Then 26.5 g (0.21 mol) of dimethyl sulfate from a dropping funnel was added within 30 minutes with stirring. The temperature rose in this connection and was held at 20° C. by cooling. A yellow suspension resulted, which was stirred another 4 hours at 20° C. and then poured with stirring in 400 g of ice water. The aqueous ethanolic suspension was stirred for 2 hours more at room temperature for the decomposition of excess dimethyl sulfate,cooled to 5° C. and filtered. The filter cake was washed with a little water and dried at room temperature in a vacuum. There was a yield of 14.1 g of yellowish crystal with a content (HPLC) of 99.9 percent (83 percent of theory, relative to malononitrile.

Workup

  1. stirringstirred for another 5 minutes at room temperature
  2. additionwere added within 60 minutes from two injection syringes
  3. additionDuring the addition
  4. customa clear yellow-green solution formed
  5. stirringwhich was stirred for another 60 minutes
  6. stirringwith stirring
  7. customwas held at 20° C.
  8. temperatureby cooling
  9. customA yellow suspension resulted
  10. stirringwhich was stirred another 4 hours at 20° C.
  11. additionpoured
  12. filtrationfiltered
  13. washThe filter cake was washed with a little water
  14. customdried at room temperature in a vacuum

Sources & evidence

ORD record
ord-b9070ce556934776b12e534443af3527
Source dataset
uspto-grants-1993_06
Patent number
US05216160

Reaction notes

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